Condensation products of the anthraquinone series



Patented June 30, 1936 UNITED STATES 2,045,817 I CONDENSATION PRODUCTS OF THE ANTHRAQUINONE SERIES Werner Ze'rweck and Ernst Honold, Frankforton-the-Main-Fechenheim, Germany, assignors to General Aniline Works, Inc., New York, N.-Y., a corporation ofDelaware No Drawing. Application January 17, 1935, Serial No. 2,304. In Germany January 20, 1934 6 Claims. (Cl. 260-44) Our invention relates to new condensation products of p the anthraquinone series, particularly those corresponding to the general formula:

wherein the benzene nucleus may be replaced by a naphthalene nucleus, n means the number 1 or 2, X stands for S or O, Y for-hydrogen or NHz, R for OH, halogen, N l-I2 or the radicle p z 0' z" wherein the Zs mean hydrogenor one of them an acylamino group and the other hydrogen The new monoand dicarboxylic" acids oi the thiazolic and oxazolic series corresponding tothe above general formula,-R- being OH, are obtain-- the presence of an organic diluent. 'The chlorides are mostly crystalline substances of a high melting point. The corresponding amides are obtainable by decomposing the chlorides by gently warming them after the addition of aqueousammonia. They are likewise crystalline substances mostly of a high melting point.

When condensing the said carboxylic acids or their halides with a-aminocompou'nds of the anthraquinone series, advantageously in the presence of organic solvents, or conversely when OOH-1 densing amides of the said carboxylicacids with a-halogen-compounds ofthe anthraquinone series, new condensation products are obtained corresponding to the above general formula, R being an aminoanthraquinonyl radicle. They are valuable vat dyestuffs of great tinctorial power Their chlorides are obtainable acwhich dye the vegetable fibers fast yellow to red to brown to violet shades.

In order to further illustrate 'ourinventionthe following examples are given; However we wish it to be understood that our invention is not limited to the particular products or reaction conditions stated therein.

Example 1- Para-aminobenzoic acid is treated according to r U. S. Patent No. 1,637,023 with disulphurdicliloride and the formed thiazthioniumchloride is saponifled, according to U. S. Patent No. 1,788,297, to the 1amino-2-mercapto-benzene-4-carboxylic' acid which may be isolated in the form of the, zinc mercaptide. For further condensation the free acid may be boiled with anthraquinone-Z-aldi hyde in the presence of a high boiling organic solvent with addition of sodium carbonate or? acetate or advantageously the solution of the anthraquinone-Z-aldehyde in about a five fold quantity of concentrated sulfuric acid may be slowly added to about a twenty-five fold amount of glacial acetic acid, and after the addition of the zincmercaptide of the ammino-mercaptobenzoic acid, the mixture may be boiled for some hours in an apparatus provided with a reflux condenser. By adding water the formed 1-(2'- anthraquinonyl) -benzothiazole-5-carboxylic acid of the formula:

C=N 5 060B 3 4 thraquinonyl) 5 chlorobenzothiazole 3 carboxylic acid of the formula:

V p O S COOH is obtained.

parts of the 1-(2'-anthraquinonyl) -benzothiazole-S-carboxylic acid chloride are mixed with 23 parts of l-amino-anthraquinone and about 300 parts of ortho-dichlorobenzene and the mixture is boiled for an hour in an apparatus provided with a reflux condenser. The condensation product which partly precipitates even when the mixture is hot is filtered off when the mixture is cold, washed and dried. It corresponds to the formula:

and dyes cotton from a dark brownish violet vat It dissolves in concen= very fast yellow shades. trated sulfuric acid with a brown color.

The same dyestufi" is formed by decomposing the 1-(2-anthraquinonyl) -benzothiazole.-5-carboxylic acid amide with l-chloro-anthraquinone' with the addition of a highly boiling diluent, an

acid binding agent such as potassium acetate and c a copper compound acting as catalyst. When acting with l-aminoanthraquinone on th 1- (2'-anthraquinonyl) -5-chlorobenzothiazole 3- carboxylic acid chloride a yellow tained.

Example 2 When 35 parts of l-amino-5-benzoylamino'-anthraquinone are condensed in the manner described in Example 1 with 40 parts of 1-(2-anthraquinonyl) -benzothiazole 5 carboxylic acid chloride a dyestufi of the formula:

is obtained. It dissolves in concentrated sulfuric acid with a brown color and dyes cotton from a dark violet vat, yellow shadesv of goodfastness, particularly to chlorine. When condensing the same carboxylic acid chloride with l-amino-- benzoylaminoanthraquinone or with I-amino-4- acetylamino-anthraquinone orange dyestuffs are obtained. When condensing one molecular pro-.

portion of 1.5-diaminoanthraquinone with two molecular proportions of the said carboxylic acid chloride, 2. yellow dyestufi is formed.

Example 3 42 parts of 1-(1'-amino-2-anthraquinonyl) benzothiazolee5-carboxylic acid chloride are condensed with 23 parts of l-aminoanthraquinone by heating with the addition of 400 parts of nitrobenzene at about 200 C. for about 1 hour. When cool the condensation product is isolated. It dissolves in concentrated sulfuric acid with ayeI- lowish brown color turning to bluish greenafter the addition of paraformaldehyde. The new dyestuif of the formula:

t dyes cotton from a blue vat, red shades of good iastness, particularly to chlorine.

When condensing 42 parts of the same carboxylic acid chloride with 35 parts of 1-amino-5- benzoylamino-anthraquinone the formed dyestuff of the fonnula'.

is obtained. It dissolves in concentrated sulfuric acid with a brown color turning to blue after the addition of paraformaldehyde and dyes cotton from a blue vat, fast reddish brown shades.

A similar dyestuff is obtained when condensing 1-amino-5-benzoylamino-anthraquinone with the chloride of the formula:

O NH: S

COCl

When using, onejcomponent. 1-amino-4-benzoylamino-anthraquinone dyestuffs are obtained which. dye reddish violet shades from a blue vat.

Example 4 When condensing 42 parts of the l-(l'-amino- 2f-anthraquinonyl) benzothiazole 5 carboxylic acid chloride with 12 parts of IA-diaminoanthraquinone' by boilinga mixture thereof with trichlorobenzene the formed condensation product .of theformula:

is obtained. It dissolves concentrated sulfuric acid with a brown color turning to blue after the addition of paraformaldehyde and dyes cotton from a blue vat fast r'eddish violet shades.

The condensation of 1'.5'-'diaminoanthraquinone with two molecular proportions of an amin'o anthraquinonyl benzo thiazole-carboxylic acid chloride yields fastbluish reddyestufis.

7 Example 5 I I and the 1-(1-amino-2-anthraquinonyl) -benzothiazole-3,5-dicarboxylic'acid can be converted into the corresponding dichloridesifor'instance by I means of thionylchloride.

46pa rts of the 1'-(2'eanthraquinonyl)Fbenzothiazole-3,5-dicarboxylicl acidvdichloride and 46;

parts of l-aiminO-anthraduinone are dissolved-in about 600 partsof nitrobenzene andthe mixture. is held whileustirring at 160'"v to 18.0"; C, for about an hour. The condensation product whichseparates even from the hot mixture;is -isolated.,.It corresponds to the formula:

1- (2' anthraquinonyl)--benzothiazolevapoiirf It isconverted intothe'chloride. 39 parts of this chloride of the formula: 1

are mixed with 23 parts of l-aminoanthraquinone and about 300 parts of o-dichlorobenzene 1 and the mixture is boiled in an apparatus provided with a reflux condenser for about an hour.

.When cool the condensation product of the f ormula is isolated. -It. dyes cotton a darlz olivee brown vat ,very fast yellow shades.

When condensing 1- (2'-anthraquinony1) benzoxazoll-carboxylic acid amide v (obtainable by decomposing the chloride with aqueous ammonia) with l-chloroanthraquinone in the presence of a high boiling diluent with the addition of an acid binding agent such 'as potassium acetate and of a copper compound acting ascatalyst the same dyestuff is obtained,- 7

When condensing 39, parts. of 1-(2'-anthraquinonyllebenzoxazole4; carboxylic aci i chloride with parts of 1-amino-5-benzoylaminoand dissolves with an orange color is" concentrated V sulfuric acid; It'dyes cotton from a brownish violet vatvery fast yellow-shades.

A more reddish yellow dyestuff is obtained when using as second component two molecular'pro- 1 portions 1 of 1-amino 5e-benzoylamino-anthraquinone.

When condensing 1-(1 -amino-2 -anthraquinonyl)-benzothiazole-3,5-dicarboxy1ic acid dichloride with two molecular,proportionsof ,1-

aminoanthraquinone aQdyestufi 'dyeing cotton fast bluish red shades is obtained.

Example 6 Equivalent amounts of 1-amino-2-hydroxy-5- benzoic acid and anthraqiiinone-iz-aldehyde are condensed by boiling for some hours with the addition of a high boiling diluent and sodium carbonateor acetate. When cool theprecipitated condensation'product is'isolated and purified by treatment with hydrochloric acid and water anthraquinone a is produced; which dyes yellow shadesifrom a dark brownish olive'vati When using 35 parts of l aminol-benzoylaminoanthraquinone, v as second component, an orange dyestuff is obtained; When condensing 1.5-diaminoanthraquinone; with two molecular. proportions of the chloride, ayel-low dyestuff is obtained.

j I Example 7 I 43 parts of 1+(2"-anthraquinonyl) 3,4-benzobenzoxazole-ficarboxylicracid chloride of the formula:

0 0 000] l l o=N 1 2 obtainable by condensing anthraquinone-2-aldehyde with 1-amino-2-hydroxynaphtha1ene-3- carboxylic acid and converting the formed acid into its chloride, are mixed with 23 parts of Laminoanthraquinone and about 400 parts of nitrobenzene and "the mixture is heated at about 200 C. for about an hour. The' condensa tion product is isolated when cold; the formula: it

o CO-HN 1 It correspondsto o ll 1.; -c:

This, dyestufi' dissolves in concentrated sulfuric I acid with a reddish brown color and dyes cotton from a dark brown vat very fast yell'ow'shades.

When using as second component I-amiho-5- benzoylamino-anthraquinone a yellowdyestufi' is formed. When using 1-ami'no-4-benzoylaminoanthraquinone an orange dystuif isobtained.

Example8 V V parts of the i-(I'-amino-2'-anthraquinonyl) 3,4 benzobenzoxazole-6 --carboxyIic acid chloride, obtainable by condensing the l-aminoanthraqtiinone-Z-aldehyd- "with l-amino 2-hy droxynaphthalene-3-ca.rboxylic acid and convert- -ing the formed aeidvinto its chloride,i.are condensed with 23v parts of l-ami'noanthraquinone' in the presence oi boiling tri'chlorobenzene. When. cold the condensation product is isolated.

5 The new dyestuff has the formula:

(I) NH:

It dyes cotton from a reddish pviolet vat fast bluish red shades.

When using 35 parts of l-amino-Ea-benzoylaminoanthraquinone as second component a fast. red. dyeing dyestufi is: obtained.

We claim:

I, Condensation products selected from the class consisting. of those corresponding to'the general formulae:

wherein 12 means the numbered 1 or 2,; X stands for S or '0, Y for hydrogen or NH-z, the Zs mean hydrogen or one of them an 'acylamine-group and; the otherhydrogen, which dyestufis dissolve in concentrated sulfuric acid with an orange to brownish color and dye the vegetable fibers from a'brownish: to violet to bluish vat fast yellowish to reddish to brownishto violet shades.

2. Condensation products corresponding to the general formula: i

wherein X stands for S or O, Y for hydrogen or NHz, the Zs mean hydrogen or one of them an acylamino-group and the other hydrogen, which dyestuffs dissolve in concentrated sulfuric acid with an orange to brownish color and dye the vegetable fibers from a brownish to violet to bluish vatfast yellowish to reddish tobrownish to violet shades;

Condensation products corresponding to the general formula:

wherein Y stands for hydrogen or NH2,' the Zs mean hydrogen. or one of them an acylamino 75 group and the other hydrogen, which dyestuffs dissolve in concentrated sulfuric acid with an orange to brownish color and dye the vegetable fibers from a brownish to violet to bluish vat 5 fast yellowish to reddish to brownish to violet shades.

4. The condensation product of the formula:

which dissolves in concentrated sulfuric acid with a brownish color and dyes cotton from a dark brownish violet vat fast yellow shades.

5. The condensation product of the formula:

S I l A which dyestufi dyes cotton from a blue vat red shades of a good fastness particularly to chlorine.

6. The condensation product of the formula:

O NH: N

which dyestufi dissolves in concentrated sulfuric acid with a brown color turning to blue after the addition of paraformaldehyde and dyes cotton from a blue vat fast reddish brown shades. 25

WERNER ZERWECK. ERNST HONOLD. 

